Scale prevention



United States Patent 8 Claims. (Cl. 252180) This application is adivision of SN. 47,386, filed August 4, 1960, now U.S. Patent No.3,200,106.

This invention relates to branched polyalkylene polyamines and toderivatives thereof. More particularly, this invention relates to saidbranched polyamines and to branched polyamines derivatives containingvarious groups, such as the oxyalkylated, acylated, alkylated,carbonylated, olefinated, etc., derivatives thereof, prepared byintroducing such groups individually, alternately, in combination, etc.,including for example, derivatives prepared by varying the order ofadding such groups, by increasing the number and order of adding suchgroups, and the like.

This invention also relates to methods of using these products, whichhave an unexpectedly broad spectrum of uses, for example, asdemulsifiers for water-in-oil emulsions; as demulsifiers foroil-in-water emulsions; as corrosion inhibitors; as fuel oil additivesfor gasoline, diesel fuel, jet fuel, and the like; as lubricating oiladditives; as scale preventatives; as chelating agents or to formchelates which are themselves useful, for example, as antioxidants,gasoline stabilizers, fungicides, etc.; as flotation agents, forexample, as flotation collection agents; as asphalt additives oranti-stripping agents for asphaltrnineral aggregate compositions; asadditives for compositions useful in acidizing calcareous strates of oilwells; as additives for treating water used in the secondary recovery ofoil and in disposal wells; as additives used in treating oil-well stratain primary oil recovery to enhance the flow of oil; as emulsifiers forboth oil-in-water and water-in-oil emulsions; as additives for slushingoils; as additives for cutting oils; as additives for oil to preventemulsification during transport; as additives for drilling muds; asagents useful in removing mud sheaths from newly drilled wells; asdehazing or fog-inhibiting agents for fuels; as additives for preparingsand or mineral slurries useful in treating oil wells to enhance therecovery of oil; as agents for producing polymeric emulsions useful inpreparing water-vapor impermeable paper board; as agents in paraffinsolvents; as agents in preparing thickened silica aerogel lubricants; asgasoline additives to remove copper therefrom; as deicing andanti-stalling agents for gasoline; as antiseptic, preservativebactericidal, bacteriostatic, germicidal, fungicidal agents; as agentsfor the textile industry, for example, as mercerizing assistants, aswetting agents, as rewetting agents, as dispersing agents, asdetergents, as penetrating agents, as softening agents, as dyeingassistants, as anti-static agents, and the like; as additives for rubberlatices; as entraining agents for concrete and cements; as anti-staticagents for rugs, floors, upholstery, plastic and wax polishes, textiles,etc.; as detergents useful in metal cleaners, in floor oils, in drycleaning, in general cleaning, and the like; as agents useful in leatherprocesses such as in flat liquoring, pickling, acid degreasing, dyefixing, and the like; as agents in metal pickling; as additives inpaints for improved adhesion of primers, in preventing water-spotting inlacquer; as anti-skinners for pigment flushing, grinding and dispersing,as anti-feathering agents in ink; as agents in the preparation of woodpulp and pulp slurries, as emulsifiers for insecticidal compositions andagricultural sprays such as "ice DDT, 24-D (toxaphene), chlordane,nicotine sulfate, hexachloroacyclohexane, and the like; as agents usefulin building materials, for example, in the Water repellent treatment ofplaster, concrete, cement, roofing materials, floor sealers; asadditives in bonding agents for various insulating building materials;and the like.

THE BRANCHED POLYAMINE The branched polyamines employed herein arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average. at least one nitrogenbonded aminoalkylene(i.e.

group per nine amino units present on the main chain, for example 1-4 ofsuch branched chains per nine units on the main chain, but preferablyone side chain unit per nine main chain units. Thus, these polyaminescontain at least three primary amino groups and at least one tertiaryamino group.

These reagents may be expressed by the formula:

RllV -RNH2 l i... J.

where n is an integer, for example 1-20 or more but preferably 1-3,wherein R is preferably ethylene, but may be propylene, butylene, etc.(straight chained or branched).

The preferred embodiments are presented by the following formula:

r H H 'l NHa(C H2O H2N) 50 The H3N(C H2O HQN) z- NH; n(n=13) Theradicals in the brackets may be joined in a headto-head or ahead-to-tail fashion. Compounds described by this formula wherein n=1-3are manufactured and sold as Polyamines N-400, N-800, N-1200 etc.Polyamine N-400 has the above formula wherein ru=1.

These compounds may be prepared by a wide variety of methods. One methodcomprises the reaction of ethanolamine and ammonia under pressure over afixed bed of a metal hydrogenation catalyst. By controlling theconditions of this reaction one may obtain varying amounts of piperazineand polyamines as we11 as the branched chain polyalkylene polyamineuseful in this invention. This process is described in Australianapplication No. 42,189, now Australian Patent No. 233,766, and in theGerman Patent No. 14,480 (March 17, 1958), reported in Chem. Abstracts,August 10, 1949, 14129.

These branched polyamines can also be prepared by to use an aromatichydrocarbon solvent of the benzene the following reactions: series.Non-limiting examples of the preferred solvent H H H 0 NO H2O HZNCHZOHZN H RC 01-1 I CI-I2-C1I2 NH,-CH2OHZNCHZCH NHQ 0=C| J=O H H H H NOH2O HZN0 H II2N NG H2O Hz-NC H2O H;N

| S0201 I I tr ethylcne tetramme 0:0 H2 0 0 o=o CH2 0:0

| I I followed by hydrolysis R (3112 R R (I111; R 011 01 Variations onthe above procedure can produce other branched polyamines.

The branched nature of the polyamine imparts unusual properties to thepolyamine and its derivatives.

For the sake of brevity and to simplify presentation, the invention willbe described by the selection of one branched polyamine to illustratethe reactions and uses thereof (i.e. N400). However, it is to beunderstood that such presentation is purely for illustration and theinvention should not be limited thereto.

ACYLATION A wide variety of acylating agents can be employed. Acylationis carried out under dehydrating condition, i.e., water is removed. Anyof the well-known methods of acylation can be employed. For example,heat alone, heat and reduced pressure, heat in combination with anazeotroping agent, etc., are all satisfactory.

The temperature at which the reaction between the acylating agent andthe branched polyalkylenepolyamine is effected is not too critical afactor. Since the reactions involved appear to be an amide-formationreaction and a condensation reaction, the general temperature conditionsfor such reactions, which are well known to those skilled in the art,are applicable.

Acylation is conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and the reactionproducts. In general, the reaction is carried out at a temperature offrom 120 to 280 C., but preferably at 140 to 200 C.

The product formed on acylation will vary with the particular conditionsemployed. First the salt, then the amide is formed. If, however, afterformingthe amide at a temperature between 140250 C., but usually notabove 200 C., one heats such products at a higher range, approximately250-280 C., or higher, possibly up to 300 C. for a suitable period oftime, for example, 12 hours or longer, one can in many cases recover asecond mole of water for each mole of carboxylic acid roup employed, thefirst mole of water being evolved during amidification. The productformed in such cases contains a cyclic amidine ring, such as animidazoline or a tetrahydropyrirnidine ring. Infrared analysis is aconvenient method of determining the presence of these groups.

Water is formed as a by-product of the reaction between the acylatingagent and the branched polyamide reactant. :In order to facilitate theremoval of this water, to effect a more complete reaction in accordancewith the principle of Le Chatelier, a hydrocarbon solvent which forms anazeotropic mixture with water can be added to the reaction mixture.Heating is continued with the liquid reaction mixture at the preferredreaction temperature, until the removal of water by azeotropicdistillation has substantially ceased. In general, any hydrocarbonsolvent which forms an azeotropic mixture with water can be used. It ispreferred, however,

are benzene, toluene, and xylene. The amount of solvent used is avariable and non-critical factor. It is dependent on the size of thereaction vessel and the reaction temperature selected. Accordingly, asufficient amount of solvent must be used to support the azeotropicdistillation, but a large excess must be avoided since the reactiontemperature will be lowered thereby. Water produced by the reaction canalso be removed by operating under reduced pressure. When operating witha reaction vessel equipped with a reflux condenser provided with a watertakeoff trap, sufficient reduced pressure can be achieved by applying aslight vacuum to the upper end of the condenser. The pressure inside thesystem is usually reduced to between about 50 and about 300 millimeters.If desired, the water can be removed also by distillation, whileoperating under relatively high temperature conditions.

The time of reaction between the acylating agent and the branchedpolyamine reactant is dependent on the weight of the charge, thereaction temperature selected, and the means employed for removing theWater from the reaction mixture. In practice, the reaction is continueduntil the formation of water has substantially ceased. In general, thetime of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products,carboxylic acids having more than 6 carbon atoms and less than 40 carbonatoms but preferably 8-30 carbon atoms give most advantageous products.The most common examples include the detergent forming acids, i.e.,those acids which combine with alkalies to produce soap or soap-likebodies. The detergent-forming acids, in turn, includenaturally-occurring fatty acids, resin acids, such as abietic acid,naturally occurring petroleum acids, such as naphthenic acids, andcarboxy acids, produced by the oxidation of petroleum. As will besubsequently indicated, there are other acids which have somewhatsimilar characteristics and are derived from somewhat different sourcesand are different in structure, but can be included in the broad genericterm previously indicated.

Suitable acids include straight chain and branched chain, saturated andunsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, andaralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic,proprionic, butyric, valeric, caproic, heptanoic, caprylic, nonacoic,capric, undecanoic, lauric, tridecanoic, myriatic, pentadecanoic,palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic,heneicosanoic, docosanoic, tri cosanoic, tetracosanoic, pentacosanoic,cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic,rnethacrylic, crotonic, anglic, teglic, the pentenoic acids, thehexenoic acids, for example, hydrosorbic acid, the heptenoic acids, theoctenoic acids, the nonenoic acids, the decenoic acids, for example,obtusilic acid, the undecenoic acids, the dodecenoic acids, for example,

lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoicacids, for example, myristoleic acid, the pentadecenoic acids, thehexadecenoic acids, for example, palmitoleic acid, the heptadecenoicacids, the octadecenoic acids, for example, petrosilenic acid, oleicacid, elardic acids, the hydroxyheptanoic acids, the hydroxy caprylicacids, the docosenoic acids, for example, erucic acid, brassidic acid,cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoicacids, for example, sorbic acid, the octadienoic acids, for example,linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, forexample, linolenic acid, eleostearic acid, pseudoeleostearic acid, andthe like.

Carboxylic acids containing functional groups such as hydroxy groups canbe employed. Hydroxy acids, par ticularly the alpha hydroxy acidsinclude glycolic acid, lactic acid, the hydroxyvaleric acids, thehydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy capryiicacids, the hydroxynonanoic acids, the hydroxycapric acids, thehydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoicacids, the hydroxymyristic acids, the hydroxypentadecanoic acids, thehydroxypalmitic acids, the hydroxyhexadecanoic acids, thehydroxyheptadecanoic acids, the hydroxy stearic acids, thehydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardicacid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, thehydroxyelcosanoic acids, for example, hydroxyarachidic acid, thehydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetylricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found inpetroleum called naphthenic acids, hydrocarbic and chaumoogric acids,cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholicacid, fenchlolic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substitutedbenzoic acids, for example, the toluic acids, the xyleneic acids, alkoxybenzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and thelike.

Mixed higher fatty acids derived from animal or vegetable sources, forexample, lard, coconut oil, rapeseed oil, sesame oil, palm kernel oil,palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow,soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil,and other fish oils, teaseed oil, partially or completely hydrogenatedanimal and vegetable oils are advantageously employed. Fatty and similaracids include those derived from various waxes, such as beeswax,spermaceti, montan wax, Japan wax, coccerin and carnauba Such acidsinclude carnaubic acid, cerotic acid, lacceric acid, montanic acid,psyllastearic acid, etc. One may also employ higher molecular Weightcarboxylic acids derived by oxidation and other methods, such as fromparaffin wax, petroleum and similar hydrocarbons; resinic andhydroarornatic acids,'such as hexahydrobenzoic acid, hydrogenatednaphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid;Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blownoils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid,cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series,for example, oxalic, malonic, succinic, glutaric, adipic, pimelic,suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylicacids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric,maleic, mesocenic, citnaconic, glutonic, itaconic, rnuconic, aconiticacids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalicacids, terephthalic acids, substituted derivatives thereof (e.g. alkyl,chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid,diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids andthe like.

Higher aromatic polycarboxylic acids containing more than two carboxylicgroups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic,pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymericacids, for example, dilinoleic, trilinoleic, and other polyacids sold byEmery Industries, and the like. Other polycarboxylic acids include thosecontaining ether groups, for example, diglycolic acid. Mixtures of theabove acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acidhalides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid isutilizable for the production of the reaction products of the presentinvention. The general structural formulae of these compounds are:

Anhydride 0 Acid CHz-C wherein R is an alkenyl radical. The alkenylradical can be straight-chain or branched-chain; and it can be saturatedat the point of un'saturation by the addition of a substance which addsto olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine,or iodine. It is obvious, of course, that there must be :at least twocarbon atoms in the alkenyl radical, but there is no real upper limit tothe number of carbon atoms therein. However, it is preferred to use analkenyl succinic acid anhydride reactant having between about 8 andabout 18 carbon atoms per alkenyl radical. Although their use is lessdesirable, the alkenyl succinic acids also react, in accordance withthis invention, to produce satisfactory reaction products. It has beenfound, however, that their use necessitates the removal of water formedduring the reaction and also often causes undesirable side reactions tooccur to some extent. Nevertheless, the alkenyl succinic acid anhydridesand the alkenyl succinic acids are interchangeable for the purposes ofthe present invention. Accordingly, when the term alkenyl succinic acidanhydride, is used herein, it must be clearly understood that itembraces the alkenyl succinic acids as well as their anhydrides, and thederivatives thereof in which the olefinic double bond has been saturatedas set forth hereinbefore. Non-limiting examples of the alkenyl succinicacid anhydride reactant are Ethenyl succinic acid anhydrides;

Ethenyl succinic acid;

Ethyl succinic acid anhydride;

Propenyl succinic acid anhydride; Sulfurized propenyl succinic acidanhydride; Butenyl succinic acid;

Z-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinicacid anhydride; Hexenyl succinic acid anhydride;

Hexyl succinic acid;

Sulfurized 3-methylpentenyl succinic acid anhydride;

2,3-dimethylbutenyl succinic acid anhydride;

3,3-dimethylbutenyl succinic acid;

1,2-dibrorno-2-ethylbutyl succinic acid;

Heptenyl succinic acid anhydride;

1,2-diidooctyl succinic acid;

Octenyl succinic acid anhydride;

Z-methyl-heptenyl succinic acid anhydride;

4-ethylhexenyl succinic acid;

2-isopropylpentenyl succinic acid anhydride;

Noneyl succinic acid anhydride;

2-propylhexenyl succinic acid anhydride;

Decenyl succinic acid;

Decenyl succinic acid anhydride;

S-methyl-Z-isopropylhexenyl succinic acid anhydride;

l,Z-dibromo-Z-ethyloctenyl succinic acid anhydri-de;

Decyl succinic acid anhydride;

Undecenyl succinic acid anhydride;

1,2-dich1or-o-undecyl succinic acid anhydride;

1,2-dichloro-un-decyl succinic acid;

3ethyl-2-t-butylpentenyl succinic acid anhydride;

Dodecenyl succinic acid anhydride;

Dodecenyl succinic acid;

2-propylnonenyl succinic acid anhydride;

3-butylocteny1 succinic acid anhydride;

Tridecenyl succinic acid anhydride;

Tetradecenyl succinic acid anhydride;

Hexadecenyl succinic acid anhydride;

Sulfurized octadecenyl succinic acid;

Octadecyl succinic acid anhydride;

1,2-dibromo-2-methylpentadecenyl succinic acid anhydride;

8-propylpentadecyl succinic acid anhydride;

Eicosenyl succinic acid anhydride;

1,2-dichloro-2methylnonadecenyl succinic acid anhydride;

2-octyldodecenyl succinic acid;

1,2-diiodotetr-acosenyl succinic acid anhydride;

Hexacosenyl succinic acid;

Hexacosenyl succinic acid anhydride; and

Hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are wellknown to those familiar with the art. The most feasible method is by thereaction of an olefin with maleic acid anhydride. Since relatively pureolefins are difiicult to obtain, and when thus obtainable, are often tooexpensive for commercial use, alkenyl succinic acid anhydrides areusually prepared as mixtures by reacting mixtures of olefins with maleicacid anhydride. Such mixtures, as well as relatively pure anhydrides,are utilizable herein.

In summary, without any intent of limiting the scope of the invention,acylation includes amidification, the formation of the cyclic amidinering, the formation of acid imides such as might occur when anhydridessuch as the alkenylsuccinic acids are reacted, i.e.

wherein P=branched polyamine residue, polymers as might occur when adicarboxylic acid is reacted intermolecularly with the branchedpolyamine, cyclization as might occur when a dicarboxylic acid reactsintramolecularly with the polyamine as contrasted to intermolecularreactions, etc. The reaction products may contain other substances.Accordingly, these reaction products are most accurately defined by adefinition comprising a recitation of the process by which they areproduced, i.e., by acylation.

The moles of acylating agent reacted with the branched polyamine willdepend on the number of acylation reactive positions contained thereinas well as the number of moles of acylating agent one wishes toincorporate into the molecule. We have advantageously reacted 1 to 10moles of acylating agent per mole of Polyamine N400, but preferably 1 to6 moles. With Polyamine N-800 and N1200, twice and three times as manymoles of acylating agent can be employed respectively, i.e. withPolyamine N800, 1-20 moles, preferably 1-12; with N-lZOO, l-30, butpreferably 1-18. Optimum acylation will depend on the particularapplication.

The following examples are illustrative of the preparation of theacylated branched polyamines.

The following general procedure is employed in acylating. The branchedpolyamine is mixed with the desired ratio of acid and a suitableazeotroping agent is added. Heat is then applied. After the removal ofthe calculated amount of water (1 to 2 equivalents per carboxylic acidgroup of the acid employed), heating is stopped and the azeotropingagent is evaporated under vacuum. The temperature during the reactioncan vary from to 200 C. Where the formation of the cyclic amidine typestructure is desired the maximum temperature is generally 180250 C. andmore than one mole of water per carboxylic group is removed. Thereaction times range from 4 to 24 hours. Here again, the true test .ofthe degree of reaction is the amount of water removed.

Example 3-A In a 5 liter, 3 necked flask furnished with a stirringdevice, thermometer, phase separating trap, condenser and heatingmantle, 1 mole (400 grams) of Polyamine N-400 is dissolved in an equalweight of xylene, i.e., 400 grams. 845 grams of oleic acid (3 moles) isadded to the polyamine with stirring in about ten minutes. The reactionmixture is then heated gradually to about C. in half an hour and thenheld at about C. over a period of 3 hours until 54 grams (3 moles) ofwater is collected in the side of the tube. The solvent is then removedwith gentle heating under reduced pressure of approximately 20 mm. Theproduct is a dark, viscous, xylene-soluble liquid.

Example 3-A The prior example is repeated except that the final reactiontemperature is maintained at 240 C. and 90 grams (5 moles) of Water areremoved instead of 54 grams (3 moles). Infrared analysis of the productindi cates the presence of a cyclic amidine ring.

The following examples of acylated branched polyamines are prepared inthe manner of the above examples from Polyamine N-40O by employing 400grams of polyamine in each example. The products obtained are dark,viscous materials.

In the examples the symbol A identified the acylated branched polyamine.Thus, specifically 1A, represents acylated Polyamine N-400, whichpolyamine is employed in all the reactions of the following table.

TABLE I.-ACYLATED PRODUCTS OF POLYAMINE N-400S Water Removed Moles GramsName do 4A1 Stearic (284) 1,136

d0 2 4A3 do 284 TABLE I.Continued Acid Moles of Water Removed Ex.Acid/Mole of Polyamine Name Grams N-40O Moles Grams Laurie (200) 600 3:13. O 54 .----d 400 2:1 2.2 40 Myristic (228.4). 685.2 3:1 5.3 95 d 2:13.0 54 4: 1 6.2 112 3:1 4. 5 81 0. 5:1 1. 9 35 0. 66:1 4. 1 74 d0 1,8003:1 6.3 113 Alkenyl (C12) 1, 064 4:1 6.1 111 succinic. Anhydride (266).798 3:1 3. 2 58 do 532' 2:1 0.3 5.4

Alkenyl (Gm) 966 3:1 5. 2 94 succim'c. Anhydride (322) 644 2:1 2.1 38...d0 644 2:1 0.2 3.6

Diphenolic (286). 858 3:1 5.0 90 --..-d0 286 1:1 1.2 22 Oiticica Oil(920 460 0. 5:1 1. 1 20 920 1:1 1. 2 22 610 5: 1 4. 7 85 366 3:1 3. 1 56do 244 2:1 2.3 41 Diglycolio (134) 134 1:1 1. 0 18 -...-d0 107.2 0.8:10.8 14 d0 67 0.511 0.5 9 Maleic anhydride 98 1:1 0.2 36

98 E do 78.4 0.8:1 0.0 -....d0 49 0. 5:1 0.1 1.8

Naphthenie (330) 990 3:1 3 54 (gSunaptic Acid 17-Ar- Terephthalic(166)... 332 2:1 4 72 17-112- ....-d0 498 3:1 5 90 17-113- -..--d0 8305:1 6 108 Chief substituent of oiticica oil is the glyceride of licanicacid:

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

For example, in demulsification extremely high alkylene oxide ratios areoften advantageously employed such as 200300 or more moles of alkyleneoxide per mole of branched polyamine. On the other hand, for certainapplication such as corrosion prevention and use as fuel oil additives,lower ratios of alkylene oxides are advantageously employed, i.e.,1:l025 moles of alkylene oxide per mole of branched polyamine. By propercontrol, desired hydrophilic or hydrophobic properties are imparted tothe composition. As is well known, oxyalkylation reactions are conductedunder a wide variety of conditions, at low or high pressures, at low orhigh temperatures, in the presence or absence of catalyst, solvent, etc.For instance oxyalkylation reactions can be carried out at temperaturesof from 80-200 C., and pressures of from 10 to 200 p.s.i., and times offrom 15 min. to several days. Preferably oxyalkylation reactions arecarried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions ofoxyalkylation reactions see U.S. Patent 2,792,369 and other patentsmentioned therein.

Oxyalkylation is too well known to require a full discussion. Forpurpose of brevity reference is made to Parts 1 and 2 of U.S. Patent No.2,792,371, dated May 14, 1957, to Dickson in which particular attentionis directed to the various patents which describe typical oxyalkylationprocedure. Furthermore, manufacturers of alkylene oxides furnishextensive information as to the use of oxides. For example, see thetechnical bulletin entitled Ethylene Oxide which has been distributed bythe Ieiferson Chemical Company, Houston, Texas. Note also the extensivebibliography in this bulletin and the large number of patents which dealwith oxyalkylation processes.

The symbol employed to designate oxyalkylation is 0. Specifically 1-0represents oxyalkylated Polyamine N-400.

In the following oxyalkylations the reaction vessel employed is astainless steel autoclave equipped with the TABLE IA.ACYLATED PRODUCTSAcid Mols of Acid Water Removed Example Branched P M015 0f PolyamineBranched N e Grams Polyamme Moles Grams 01810 (282) 564 2:1 dn 282 1:11,800 311 0 1,200 2:1 Alkenyl Succinic Anhydride (266)--. 532 2:1

do 266 L;L Diglycolic (134) 134 1:1 1. 0 18 Maleic Anhydride (98) 98Naphthenic (33) Sunaptic Acid B... 330 1:1 2.1 37.8 Acetic (6 1: 1. 119. 6 Diphenolic (286)-- 286 1:1 1. 1 19. 6 Stearic (284)...- 568 2:1 1.8 32. 4 0 284 1:1 1.9 34.2 Dimeric (600) 600 1:1 1. 1 19. 6 Benzoic(122) 122 1:1 0.9 16. 2 Terephthahc (166) 166 1:1 0. 8 14. 4 Diphenolic(286).. 286 1:1 1. 0 18. 0 Laurie (200) 200 1:1 1. 2 21. 6 32-11 N-1200Oleic (282) 8 6 3:1 3. 1 55,8 32-1 N-1200 do 564 2:1 1.9 34. 2 32AN-1200 do 282 1:1 1.0 18. 0 33-A N-1200 Acetic (60) 0 4:1 4. 0 72. 0

OX YALKYLATION usual devices for heatmg and heat control, a stirrer,inlet These branched polyamines can be oxyalkylated in the conventionalmanner, for example, by means of an alphabeta alkylene oxide such asethylene oxide, propylene oxide, butylene oxide, octylene oxide, ahigher alkylene oxide, styrene oxide, glycide, methylglycide, etc., orcombinations thereof. Depending on the particular application desired,one may combine a large proportion of alkylene oxide, particularlyethylene oxide, propylene oxide, a combination or alternate additions orpropylene oxide and ethylene oxide, or smaller proportions thereof inrelation to the branched polyamine. Thus, the molar ratio of alkyleneoxide to branched polyamine can range within wide limits, for example,from a 1:1 mole ratio to and outlet means and the like which areconventional in this type of apparatus. The stirrer is operated at aspeed of 250 r.p.m The branched polyamine, Polyamine N-400, dissolved inan equal Weight of xylene is charged into the reactor. The autoclave issealed, swept with nitrogen, stirring started immediately and heatapplied. The temperature is allowed to rise to approximately C. at whichtime the addition of the alkylene oxide is started and addedcontinuously at such speed as it is absorbed by the reaction mixture.When the rate of oxyalkylation slows down appreciably, which generallyoccurs after about 15 moles of ethylene oxide are added or after about10 moles of propylene oxide are added, the reaction vesa ratio of1000zl, or higher, but preferably 1 to 200. 7 sel is opened and anoxyalkylation catalyst is added (in 2 Ill weight percent of the totalreactants present). The catalysts employed in the examples is sodiummethylate. Thereupon the autoclave is flushed out as before andoxyalkylation completed. In the case of oxybutylation, oxyoctylation,oxystyrenation, and other oxyalkylations, etc., the catalyst is added atthe beginning of the operation. Example 1-0 Using the oxyalkylationapparatus and procedure stated above, the following compounds areprepared: 400 grams (1 mol) of Polyamine N400 are charged into astainless steel autoclave, swept with nitrogen, stirring started, andautoclave sealed. The temperature is allowed to rise to approximately100 C. and ethylene oxide is injected continuously until 220 grams mols)total had been added over a one-half hour period. This reaction isexothermic and requires cooling to avoid a rise in temperature. Thereaction mass is transferred to a suitable container. Upon cooling toroom temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-0 The same procedure as Example l-O is used exactly exceptthat 396 grams of ethylene oxide (9 mols) is added to 400 grams (1 mol)of Polyamine N400. This reaction material is a dark viscous liquid atroom temperature.

Example 1O The same procedure as Example 1-0 is used and 396 grams ofethylene oxide (9 mols) are added to 400 grams (1 mol) of PolyamineN400. After this reaction is completed, the autoclave is opened and 20grams of sodium methylate are added. The autoclave is then flushed againwith nitrogen and an additional 572 grams (13 mols) of ethylene oxide isadded at 100 C. This reaction is highly exothermic. The reaction massnow contains 1 mol of N-400 and a total of 22 mols of reacted ethyleneoxide.

Example ]O,;

A portion of the reaction mass of Example 1O is transferred to anotherautoclave and an additional amount of EtO was added. The reaction massnow contains the ratio of 1 mol of N400 to 40 mols of EtO.

Example 17-0 12 continued until a molar ratio of 1 mol of N-400 to 75mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to Example 1-O is continueduntil a molar ratio of 1 mol of N400 to 83 mols of EtO is reached.

20 each mol of N-400. It is a dark very viscous liquid at 1'0 0mtemperature.

Example 2-0 The addition of propylene oxide to 2-0 is continued asfollows: The autoclave is opened and 35 grams of sodium methylate areadded. The autoclave is again purged with nitrogen and sealed. Propyleneoxide is added carefully until an additional 290 grams have beenreacted. A sample is taken at this point and labeled 2-0 This compoundnow contains l0 mols of propylene oxide for each mol of N-400.

sample is taken at this point and labeled 2-0 Example 2-0 Theoxypropylation of 2-0 is continued until an additional 638 grams ofpropylene oxide are reacted. A

contains 21 mols of propylene oxide for each mol of N-400. At roomtemperature the product is a dark thick liquid.

This oxyalkylation is continued to produce examples A summary ofoxyalkylated products produced from N-400 is presented in the followingTable II.

The Roman numerals (I), (II), and (III) beside the moles of oxide addedindicate the order of oxide addi- The addition of ethylene oxide toExample 1-O is 5 t-ion (I) first, (II) second and (III) third, etc.

TABLE II.OXYALKYLATED PRODUCTS [Moles of oxide/mole of N-400] Ex. EtOWgt Moles (g.)

Pro Wgt.

BuO Wgt. Moles (g.)

Physical properties Moles (g.)

Dark viscous liquid.

Semi-solid. Solid.

(III). I,

Semi-solid. Dark thick liquid.

D0. D0. Solid. Dark viscous liquid.

Do. Do. Do. 980 (I) 4, 350 Do. Octylene oxide, 5 moles, 63' g. Do.Octylene oxide, 8 moles, 1016 g. Do. Styrene oxide, 4 moles, 480 g. D0.Styrene oxide, 7 moles, 840 g. D 0. Epoxide 201, 1 mole, 280 g. Sohd.

13 14 r The following table presents specific illustration of ACYLATIONTHEN OXYALKYLATION compounds other than N400 and its derivatives. P 1 db h d 1 b 1k 1 I101 acy ate ranc e p yammes [can e oxya y EIIA. XYALKYATED PRODUCTS TABL O L ated in the above manner by starting with theacylated M018 Dioxide Per M01 of branched po1yamine instead of theunreacted amine. Branched Bra ed Polyamine y a Non-l1m1t1ng examples arepresented 1n the following Example Polyamme Proper les tables. Thesymbol employed to designate an acylated, Eto Pro Buo oxyalkylatedbranched polyamine is A0. Specifically 1A O represents acylated, thenoxyalkylated polyfg Y 1O amine N-400.

Example 3-A 0 Solid.

Do. For this example an autoclave equipped to handle alkyl- %3 eneoxides is necessary. 1156 grams (1 mole) of 3-A f ig (N400+3 moles oleicacid minus three moles H O) are Dd' charged into the autoclave.Following a nitrogen purge g2: and the addition of 120 grams ofsodium.methylate, the %0- temperature is raised to 135 C. and 5683 gramsof EtO 3: (98 mols) are added. At the completion of this reaction, 2024grams of PrO (46 moles) are added and the reac- Do: tion allowed to goto completion. The resulting polymer 3g; is a dark viscous fluid solublein an aromatic solvent. D0. 5336s Example -4 3 liquid.

3g: For this example a conventional autoclave equipped to handlealkylene oxides is necessary. 946 grams of 1 3 5-A (N-400+3 moles lauricacid minus 3 moles H 0) 3 are charged into the autoclave. The charge iscatalyzed 0- Do. with 100 grams of sodium methylate, purged withnitrogen 5 octylene 3 5 mols 2g; and heated to 150 C. 480 grams (4moles) of styrene ggflgnw st rene niols B oxide are added and reactedfor 24 hours with agitation. 0 5 pom e mos 3: The resulting product is adark extremely viscous fluid.

Do. D0. D0. Example 7A O B0. 0. B For this example a conventionalautoclave equipped O. Do. to handle alkylene oxides is necessary. 1314grams of 53; 7-A (N-400+4 moles palmitic acid minus 6.2 moles g8 H O)are charged into the autoclave. Following the D0: addition of 120 gramsof sodium methylate and a nitrogen g3: purge, the mass is heated to 135C. 660 grams of EtO Do. (15 moles) are added and the reaction proceededto com- B3; pletion. Then 1440 grams of BuO (20 mols) are added Bgandagain the reaction proceeded to completion. The re- (1% D0: sultingpolymer is a dark viscous fluid soluble in an 200 5 111 4 1 2 D -imm Styrene rime, 5m 1s Solid 5 aromatlc f N12 tr de s D These reactions aresummarized 1n the following table:

TABLE III.ACYLATED, OXYALKYLATED N-400 [Moles oi oxide/mole oi reactant]EtO PrO B Ex. Physical Properties Dark, viscous liquid.

2 (I) 116 3 (II) 216 Do. Styrene oxide, 4 moles, 480 grams Dark, viscousliquid. Octylene oxide, 5 moles, 635 grams Do. 660 20 (II) 1,440 Dark,thick liquid. 440 30 (I) Do.

4,796 210 (I) Do.

1,018 26 (II) Do. 9A3O3 36 (II). 1,584 78 (I) Do. 11A1O1.. 32 (I) 1, 40823 (II) Solid.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE III-A.AOYLATED, OXYALKYLAIED BRANCI-IED POLYAMINES Mols t OxidePer MOI of Rcactant Example Physical Properties EtO PrO BuO 18AzO1 Dark,viscous liquid. 18AzO2.. D0. 18-A303..-- D0. 18AzO-1 (I) DO. 18A305 eneoxide, 4 mols Do. 22A1O1- (11).--. Do. A101- 2 (I) DO. 25-1102" mols Do.26A1O1-.- 10 (III)- Do. 26A1Oz Do. 26A103 4 D0. 27A101- 1 (III) D0.27A10z 15 DO. 27A10a D0- 27A1O4 D0. 28A1O1 26 (I) Do. 31A1O1 DO. 31A102D0. 31A103 3 D0. 31-A1O4 Epoxidc 201, 1 mol Do. 33A101.... Styreneoxide, 10 mols Do.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated branched polyaminescan be acylated with any of the acylation agents herein disclosed (incontrast to acylation prior to oxyalkylation). Since these reactantsalso have hydroxy group acylation, in addition to reaction with theamino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried outwith the polyamine itself, i.e., dehydration wherein the removal ofwater is a test of the completion of the reaction.

Example 1-O A One mole of 1O (620 grams) is mixed with three moles ofacetic acid (180 grams) and 400 ml. of xylene at room temperature. Thetemperature is raised slowly to 120-130 C. and refluxed gently for onehour. The temperature is then raised to 150160 C. and heated until 3moles of water and all of the xylene are stripped oflf. The dark productis water-soluble.

Example 2O A One mole of 2O (2894 grams) is mixed with one mole ofpalmitic acid (256 grams) at room temperature. Vacuum is applied and thetemperature is raised slowly until one mole of water (18 grams) isremoved. This product is a dark viscous liquid.

Example 6O A One mole of 6O (7450 grams) is mixed with 500 grams ofxylene and heated to 100 C. One mole of diglycolic acid (134 grams) isadded slowly to prevent excessive foaming. The temperature is raised to140150 C. and held until one rnole of water has evolved. This product isthe diglycolic acid fractional ester of 6O A white precipitate formsduring this reaction which can be removed by filtration. Analysis showsthe precipitate to be sodium acid diglycollate, a reaction product ofthe catalyst and diglycolic acid. The filtered product is a dark viscousliquid at room temperature.

Table IV contains examples which further illustrate the invention. Thesymbol employed to designate oxyalkylated, acylated products is "'OA.

TABLE IV.OXYALKYLATED, THEN ACYLATED BRANCHED POLYAMINE N-400 AcylatingAgent Water Removed Ex. Physical Properties Moles of Wgt. Wgt. NameAcylating Grams Moles (g.)

Agent 1-O1A Acetic 3 180 3 54 Darkliquid. 1-o21 0181c 1 282 1 18 Do.lO1A Stcarlc 1. 2 568 2 36 Solid. 2-0121" Lauric 1 200 1 18 Darkliquid.2-0 11. Myristic 2 457 2 36 Do. 2-0111 Palmiticufl 1 256.4 1 18 Do.4=O1A Olcic 2 564 2 36 Solid. 4-0211 Ricinolcic-.. 1 298.5 1 18Darkliquid. 5O1A Abictic acid, 1 302. 4 1 18 Dark solid. 5O3A Tall011..., 1 175 1 18 Darkliquid. 6O1A Linoleic 1 280.4 1 18 D0. c0 11.-Olcic 2 564 2 36 Do. 6OsA Maleic an 1 98 1 18 Viscous hydride. liquid.6-0511 Diglycolic-.- 1 134 1 18 Do. 7-0111. Laurie 2 400 2 36 Darkliquid. 8-O1A. Stearic 1 284 1 18 Solid.

The following table presents specific illustration of compounds otherthan N400 and its derivatives.

TABLE IVA.-OXYALKYLATED, THEN ACYLATED BRANCI'IED POLYAMINE Water Molsof Removed Ex- Name Acylating Wt. in Physical ample Agent GramsProperties Mols Wt. in grams 10-O3A- Stcaric 1 284 1 18 Solid. 11-OzALaurie 2 400 2 36 Viscous liquid. ll-QuA- Diglycolic 1 134 1 18 Darkliquid. 12O1A Maleic an- 1 98 Viscous hydride. liquid 13-011 1- Oleic 1.2 564 1 18 Do. 14-0 11- Linoleic 1 280.4 1 18 Do. 15-0111- Tall o1l 1175 1 18 Do 16-O3A. Abietic acid 1 302 1 18 Solid 17OA Ricinolcic... 1298 1 18 Viscous .liquid 18OA Olcic 2 564 2 36 Do. 20-0111- Palmitic 1256 1 18 Solid. 20-O5A Myristic 2 457 2 36 Do. 21O1A Laurie 1 200 1 18Do. 21-0611. Stcaric 2 568 2 36 Do. 22-0211. Oleic 1 282 1 18 Viscousliquid 23-02A Acetic 1 60 1 18 Do. 24-O A. Diphenolic 1 286 1 18 Do.25-0111. Terephthalic 1 166 1 18 Solid. 25O4A Napththenic 2 330 2 36Viscous liquid 25-O6A- d0 1 330 1.9 34 Do. 26-0111. Bcnzoic 1 122 1 18Do. 26-O3A. Laurie 1 200 1.8 32 Do HEAT TREATMENT OF O-XYALKYLATEDPRODUCTS The oxyalkylated products described herein, for example, thoseshown in Table *II relating to oxyalkylated branched polyamines andthose in Table III relating to oxyalkylated, prior acylated, branchedpolyamines can be heat treated to form useful compositions.

In general, the heat treatment is carried out at 200- 250 C. Underdehydrating conditions, where reduced pressure and a fast flow ofnitrogen is used, lower temperatures can the employed, for example -200C.

Water is removed during the reaction, such as by means of a side trap.Nitrogen passing through the reaction mixture and/ or reduced pressurecan be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulasfor the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of thesecompounds and is effected by heating same at elevated temperatures,generally in the neighborhood of 200-270 C., preferably in the presenceof catalysts, such as sodium hydroxide, potassium hydroxide, sodiumethylate, sodium glycerate, or catalysts of the kind commonly employedin the manufacture of superglycerinated fats, calcium chloride, iron andthe like. The proportion of catalyst employed may vary from slightlyless than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed duringthe process. At times the process can be conducted most readily bypermitting part of the, volatile constitutents to distill, andsubsequently subjecting the vapors to condensation. The condensedvolatile distillate usually contains water formed by reac tion. Thewater can be separated from such condensed distillate by any suitablemeans, for instance, distilling with xylene, so as to carry over thewater, and subsequently removing the xylene. The dried condensate isthen returned to the reaction chamber for further use. In someinstances, condensation can best be conducted in the presence of ahigh-boiling solvent, which is permitted to distill in such a manner asto remove the water of reaction. In any event, the speed of reaction andthe character of the polymerized product depend not only upon theoriginal reactants themselves, but also on the nature and amount ofcatalyst employed, on the temperature employed, the time of reaction,and the speed of water removal, i.e., the efiectiveness with which thewater of reaction is removed from the combining mass. Polymerization canbe effected without the use of catalysts in some instances, but suchprocedure is generally undesirable, due to the fact that the reactiontakes a prolonged period of time, and usually a significantly highertemperature. The use of catalyst such as iron, etc.

fosters the reaction.

The following examples are presented to illustrate heat treatment. Thesymbol used to designate a heat treated oxyalky-lated polyamine is OHandan acylated, oxyalkylated product is AOH. In all examples 500 grams ofstarting material and a temperature of 225250 C. are employed.

Example 1-O H Example 2-O H The process of the immediately previousexample is repeated using 2O but substituting sodium methylate forcalcium chloride. The product is a dark, viscous, watersoluble material.

Example 6-O H The process of Example 1O H is repeated using 6-0 butsubstituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (l) OXYALKYLATED'AND (2) ACYLATED, OXYALKYLATEDPOLYAMINE N-400 All of the above products are dark, viscous liquids.

The following table presents specific illustrationof compounds otherthan N-40O 'and its derivatives.

TABLE VA.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATEDBRANCHED POLYAMIN Example Catalyst (5 grams) Wt. of Water Mols of H10Time in Removed Removed Hours 31 1. 7 7. 5 61 3. 4 8. 0 33 l. 8 6. 8 633. 5 8.0 47 2. 6 8. 5 27 1. 5 7. 5 50 2. 8 8. 0 54 3.0 8. 5 40 2. 2 10.056 3:1 9.3 63 3. 5 8.0 58 3. 2 7. 5 29 1. 6 8. 5 18A20aH 50 2. 8 7. 525.A.1OzH 29 1.6 8. 5 26A1OnH 63 3. 5 h 8.0 27A 1OaH 33 1.8 6.8 31A102H.27 1. 5 7. 5 33AiOiH (lo 50 i 2.8 8.0

All of the above products are dark, viscous liquids.

ALKYLATION Alkylation relates to the reaction of the 'branched polyamineand derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl, etc,halides which contains at least one carbon atom and up to about thirtycarbon atoms or more per molecule can be employed to alkylate theproducts of this invention. It is especially preferred to use alkylhalides having between about one to about eighteen carbon atoms permolecule. The halogen portion of the alkyl halide reactant molecule canbe any halogen atom, i.e., chlorine, bromide, fluorine, and iodine. Inpractice, the alkyl bromides and chlorides are used, due to theirgreater commercial availability. Nonlimiting examples of the alkylhalide reactant are methyl chloride; ethyl chloride; propyl chloride;n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide;isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride;2-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide;7-ethyl-2-methyl-undecyl i0- dide; tetradecyl bromide; hexadecyl bromidehexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosylchloride; tetracosyl iodide; hexacosyl bromide; octacosyl 19 chloride;and triacontyl chloride. In addition, alkenyl halides can also beemployed, for example, the alkenyl halides corresponding to the aboveexamples. In addition, the halide may contain other elements besidescarbor and hydrogen as, for example, where dichloroethylether isemployed.

The alkyl halides can be chemically pure compounds or of commercialpurity. Mixtures of alkyl halides, having carbon chain lengths fallingwithin the range specified hereinbefore, can also be used. Examples ofsuch mixtures are mono-chlorinated wax and mono-chlorinated kerosene.Complete instructions for the preparation of mono-chlorowax have beenset forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and the branchedpolyamine is a condensation reaction, or an alkylation reaction,characterized by the elimination of hydrogen halide, the generalconditions for such reactions are applicable herein. It is preferable tocarry out the reaction at temperatures of between about 100 and about2500 C., preferably between about 140 C. and about 200 C., in thepresence of a basic material which is capable of reacting with thehydrogen halide to remove it. Such basic materials are, for example,sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines,alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the alkyl halidereactant and the branched polyamine reactant in a hydrocarbon solventunder reflux conditions. The aromatic hydrocarbon solvents of thebenzene series are especially preferable. Non-limiting examples of thepreferred solvent are benzene, toluene, and xylene. The amount ofsolvent used is a variable and non-critical factor. It is dependent onthe size of the reaction vessel and on the reaction temperatureselected. For example, it will be apparent that the amount of solventused can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and the branchedpolyamine is dependent on the Weight of the charge, the reactiontemperature selected, and the means employed for removing the hydrogenhalide from the reaction mixture. In practice, the reaction is continueduntil no more hydrogen halide is formed. In general, the time ofreaction will vary widely such as between about four and about tenhours.

It can be postulated that the reaction between the alkyl halide reactantand the branched polyamine results in the formation of products wherethe alkyl group of the alkyl halide has replaced a hydrogen atomattached to a nitrogen atom. It is also conceivable that alkylation ofan alkylene group of the branched polyamine can occur. However, theexact composition of any given reaction product cannot be predicted. Forexample, when two moles of butyl bromide are reacted with one mole ofPolyamine N-400, a mixture of mono-, di and tri and higher N-alkylatedproducts can be produced. Likewise, the alkyl groups can be substitutedon different nitrogen atoms in different molecules of the branchedpolyamine.

Thus, the term alkylation as employed herein and in the claims includesalkenylation, cycloalkenylation, aralkylation, etc., and otherhydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkylhalide with the branched polyamine at the desired ratio in the presenceof one equivalent of base for each equivalent HCl given off during thereaction. Water formed during the reaction is removed by distillation.Where the presence of the anions, such as chlorine, bromine, etc., isnot material and salts and quaternary compounds are desired, no base isadded.

The following examples are presented to illustrate the alkylation of thebranched polyamines.

20 Example 5-K;

One mole of each of the following: tetradecylchloride, Polyamine N-400,and sodium bicarbonate are placed in a reaction vessel equipped with amechanical stirrer, a thermometer and a condenser reflux take-off forremoval of water from the reaction as it is evolved in an azeotropicmixture of water and a hydrocarbon solvent. The reflux take-off isfilled with xylene. The stirred reactants are heated to about C.whereupon an exothermic reaction causes the temperature to rise to aboutC. The reaction temperature is then increased to 160 C. and held therefor two hours. Then, xylene is added to the reaction vessel in an amountsufficient to cause a xylene reflux to take place at a temperature of-170 C. The reaction is continued for six hours or until the theoreticalamount of water is removed. Thereupon, an equal volume of xylene isadded to the reaction mixture and the resultant solution is filtered.This filtrate is then evaporated under reduced pressure to yield a darkamber oil. No halogen was present in this product as evidenced by anegative Beilstein copper wire test.

Example 5-K X The above reaction is repeated except that no sodiumbicarbonate is employed in the reaction. The reaction product containedchlorine.

The reactions shown in the following table are carried out in a similarmanner. Each reaction in the table is carried out in two ways(1) in thepresence of base as in 5-K to yield the halogen-free alkylation product,Table VI, and (2) in the absence of base to yield halogen containingproducts in the manner of S-K X, Table VII.

The alkylated products of this invention contain primary, secondary,tertiary, and quaternary amino groups. By controlling the amount ofalkylation agent employed and the conditions of reaction, etc., one cancontrol the type and amount of alkylation. For example, by reaction lessthan the stoichiometric amount of alkylation agent one could preservethe presence of nitrogen-bonded hydrogen present on the molecule and byexhaustive alkylation in the presence of suflicient basic material, onecan form more highly alkylated compounds.

The moles of alkylating agent reacted with the branched polyamine willdepend on the number of alkylation reactive positions contained thereinas Well as the number of moles of alkylating agent one wishes toincorporate into the molecule. Theoretically every hydrogen bonded to anitrogen atom can be alkylated. We have advantageously reacted 1-10moles of alkylating agent per moles of Polyamine N-400, but preferably1-6 moles. With Polyamine N-800 and N-1200, twice and three times asmany moles of alkylating agent can be employed nespectively, i.e., withPolyamine N-800, 1-20 moles, preferably 1-12; with Polyamine N-1200,1-30 but preferably 1-18. Optimum alkylation will depend on theparticular application.

In addition, the alkyl halide may contain functional groups. Forexample, chloroacetic acid can be reacted with the branched polyaminesto yield a corn-pound containing carboxylic acid groups PN-CH COOH,wherein P is the residue of the polyamine.

In addition, the branched polyamine can be alkylated with an alkylhalide such as alkyl chloride and then reacted with chloroacetlic acidto yield an alkylated polyamine containing carboxylic acid groups Thesymbol employed to designate an alkylated polyamine is K. Where theproduct is a salt or a quarternary the symbol is KX.

TABLE VL-ALKYLATED PRODUCTS Ratio, Moles of Ex. Alkylating AgentAlkylating Agentl- Physical Mole of Polyarnine Properties 400 orDerivatives 5 1-K1 Butyl chloride 1:1 Viscous liquid 1-K2 ..'..do 3:1Do. 5:1 D0. 2:1 D0. 4:1 D0. 6:1 D0. 3:1 Do. 5:1 D0. 7:1 D0. 2: 1Semi-solid. 3:1 D0. 5:1 Solid. 1:1 Semi-solid. 3:1 Solid. --..-do. 6:1Do.

Octadecyl chlori e. 1:1 Semisolid. -.--.do 3:1 Solid. .do 4:1 Do.

Benzyl chloride 1:1 Viscous liquid. .-..-do 5:1 Solid. .---.do 3:1 Do.

Allyl chloride 3:1 Viscous liquid. .----do 4:1 Do. .-...do 6:1 Do.Dodcoenyl chloride- 1:1 Do. .---.do 3:1 Semi-solid. .-..-do 5:1 Do. Dodecylbenzyl 2: 1 Solid.

chloride. 4:1 Do. .....do :1 Do.

1,4-dichlorobutene-2. 1 :2 Viscous liquid. -----d0 2:1 Do. ..-..do 3:1Do. 1,4xylylene 1:2 Do.

dichloride. o 3:1 Do. do 5:1 Do. Dichlorodiethylether. 1 1 Do. .-.-.do3:1 Do.

Dichloro diethylether. 5: 1 Semi-solid Benzylchloride 8:1 1d. Methylchloride-- 6:1 Liquid. Dimethylsuliate 4: 1 D o. Ethylene dichloride..-2:1 Viscous liquid. 1,4-dichlorobutene-2..- 4:1 Do. Dodecyl chloride 3:1Semi-solid. 7A1OrK n-Amylbromide 4:1 Viscous liquid. 4-OzHK 1,4-xylylene3:1 D0.

dichloride. 6-0111]; Methyl chloride 6:1 Liquid. 7-A1O2HK.--.Dich1orodiethylether.. 4:1 vilsconsi lqul 11Ar01HK.- ..---do 4:1 Do.

The following table presents specific illustration of compounds otherthan N-400 and itsderivatives.

TABLE VIA.ALKYLATED PRODUCTS Alkylating Agent Ratio Moles of AlkylatingAgent/of Polyamine N400 or derivative Physical Properties Butyl chloride1,4-dichlorobuten 1,4-grylylene dichlo de.

ride. .-.do

. .do Dicliilorodiethyleth r.- o

Dichlorodiethylether. Benzylchlorid Methyl chlori Dimethy1sulfate......-

Ethylene dichloride. 1,4-dichlorbutene-2. Dodecyl chloride.n-Amylbromide 1,4-xylylene dichloride. Methyl chloride.

Dichlorodiethylet r .....do

Do. Semi-solid. Solid.

Do. Liquid. Viscous The following table presents specific illustrationof compounds other than-N -40O and its derivatives.

Ratio, Mols of Branched Alkylating Agent Physical Example PolyamineAlkylating Agent Per Mol of Properties Branched Polyaminc or Derivatives14-K1 N-800 Benzyl chloride 2: 1 Viscous liquid. 14-Kr N-800 -.do 3:1Do. do 5: 1 Do. Dichlorodiethylether.--- 1: 1 Semisolid 15-1 N-8fl 3:1Do.

Allyl chloride 1:1 Viscous liquid 2:1 D0. 3: 1 DO. 1 1 Do. 3:1 Do.-.do..-.. 5:1 Do. Methyl chl 6:1 Do. n-Amyl bromide- 3:1 Do. Dodecenylchloride- 1 1 Do. Dimethyl sulfate..-- 2:1 Do. Dichlorodiethylether.. 1:1 Do. 26-A1O N-12nn Allyl chloride 2: 1 D0. 33A1O1K---- N-1200 Octadecylchloride-- 3:1 D0. 11-O AK N-iznn n-Amyl bromide-- 1:1 Do. 18-O A N-nBenzyl chloride. 2: 1 Do. 14O HK.- N-1200 Dichloropentane-.. 1:1 Do.25ArO1HK-- N-1200 Methyl chloride 1 :1 Do.

TABLE VIIA.SALI AND QUATERNARY PRODUCTS OF %]IR%%LATED BRANCHEDPOLYAMINE AND DERIVA- Ratio of Alkylating Physical Example AllrylatingAgent Agent/of Properties Polyarnine or Derivative l4-K1X Ethylenedichloride. 2:1 Solid. 14-KzX n Arnyl bromide 3:1 Do. 14-K3XDichlorodiethylethen. 4:1 Do. 15-K1X Dimethyl sulfate 3:1 Do. 15-KzX 1,Methyl chloride 2:1 Do. 16-K1X 1,4-xylene dichloride. :1 Do.

16-K2X Dolecylbenzyl ehlor- 8:1 Semi-solid.

16-K3X 1,4-dichlor0butene-2 3:1 Do. 17-K1X Benzyl chloride 4:1 Do.17-K2X Methyl chloride 7 3:1 Do. lT-KaX Ethylene dichloride 2:1 Do.18-AQKX Dodecyl chloride 1:1 D0. 31-A1KX Dichlorodiethylether 1:1 Solid.-03KX Benzyl cl1loride 3:1 Do. 11-O4KX .d0 2:1 Do. do.-. 1:1 Do. Methylchloride 5:1 Do. .do 4:1 Do. .do 3:1 Do. Dichlorodiethylether. 3: 1 Do...do 2:1 Do. 25A102HKX ..do 1:1 Do.

ALKYLATED THEN ACYLATION The alkylated material prepared above can befurther treated with acylating agent where residual acylatable aminogroups are still present on the molecule. The acylation procedure isessentially that described above wherein carboxylic acids react with thealkylated polyamine under dehydrating conditions to form amides andcyclic amidines. The product depends on the ratio of moles of Waterremoved for each carboxylic acid group, i.e., 1 mole water/l molecarboxylic essentially amides; more than 1 mole Water/l mole carboxylicacid group, essentially cyclic :amidines, such as imidazolines.

Such compounds are illustrated in the following table. The symbolemployed to designated alkylated acylated products is KA and acylated,alkylated, acylated products is AKA.

PNH CHz=0H( ioR PNCHzOHzC-OR Where the compound contains an additionalactive hydrogen, other unsaturated molecules can be added to theoriginal molecule for example:

PN=(CHzCHz( lOR) Where one or more active hydrogens are present atanother reactive site, the following reaction could take place:

0 0 R0 (IECHC Hz-NP (NCHgO H% o R) n The reaction is carried out in theconventional manner such as illustrated, for example, in SyntheticOrganic Chemistry, Wagner & Zook (Wiley, 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted withthe polyamine and derivatives thereof including thefollowing-acrylonitrile, acrylic and methacrylic acids and esters,crotonic acid and esters, cinnamic acid and esters, styrene, styrenederivatives and related compounds, butadiene, vinyl ethers, vinylketones, maleic esters, vinyl sulfones, etc.

In addition, the polyamine and derivatives thereof containing activehydrogens can be used to prepare telomers of polymer prepared from vinylmonomers.

The following are examples of olefination. The symbol employed todesignate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glassresin apparatus. Since the reaction is that'of a double TABLEVIIL-ACYLATED, PRIOR ALKYLATED BRANCHED POLYAMTNES Moles of AcylatingMoles Water Physical Ex. Acylating Agent Agent/Mole of N Wgt. RemovedProperties 400 or Derivative 2 564 3. 1 Vicsous liquid.

3 852 3.0 Solid.

2 400 2. 8 Viscous liquid.

3 769 4.1 Do. 5-KzA Dimeric 1 600 2. 2 Do. 6-K A Alkenyl (C12) succinic1 266 0.5 Solid.

anhydride. 7-KzA Oleic 1 282 1. 7 Viscous liquid.

2 598 3. 0 Do. 1-0 KA Oleic 1 282 1.5 Do. 3-A3KA Alkenyl (C12) succinic1 266 Solid.

anhydride. 3-A3KAz. Oleic 1 282 1. 5 Viscous liquid.

The following table presents specific illustration of compounds otherthan N-400 and its derivatives.

TABLE VIII-A.ACYLATED, PRIOR ALKYLATED BRANCHED POLYAMINE Mols ofAcylating Wt. of Acyla- Mols of Physical Example Acylating AgentAgent/M01 of ting Agent Water Properties Polyamine or Used RemovedDerivative 14K1A Laurie 1 200 1.1 Solid.

15-TGA Ricinoleic 3 894 3. 0 D0. 16-1? A 0leic. 2 564 3. 5 Do. 17-KzA 2512 2. 0 D0. 18AzKA 1 568 1. 0 Do. 10-O3KA- 1 282 1. 0 Do. 2506KA- 2 5602.0 Do. 26-AlO2KA 1 1. 5 Do. 11-OzAKA--. 1 134 1.0 Do. 14-O HKA 2 196Do. 25A1O2HKA Ole 1 282 1. 5 Do.

bond with an active hydrogen, no water is eliminated. The reaction isrelatively simple, as shown by the following example:

Charge 400 grams of N-400 (1 mol) into glass resin 26 CARBONYLATIONCarbonylation relates to the reaction of the branched polyamine andderivatives with aldehydes and ketones. Where primary amino groups arepresent on the poly apparatus. Care should be taken that the N-400 iswater- 5 free, to eliminate undesirable side reactions At room aminoreactants, Schrfls bases can be formed on reaction temperature, slowlyadd 53 grams of acrylonitrile (1 mol). Wlth carbonyl corPPounds- 9 exampWhere an alge- The reaction proceeds smoothly without the aid of a hyde'F as saihcylaldehyde 1S reacted wlth Polyamme catalyst Warm gently to804000 and Stir for one N-400 1n a ratio of 3 moles of aldehyde to 1mole of houn 10 Polyamine, the following type of compound could beExample 6-U formed:

H H H H To 800 grams of N-400 (2 mols) m 800 grams of xy- G=N-(CHzCH2N)CHzOH2N-OHCHzNOHzCHzN=C lene, add 124 grams of divlnyl sulfone (1 mol)at room I temperature. This reaction is exothermic and care must 11 g 2OH be taken to prevent an excessive rise in temperature which 15 I wouldcause cross-linking and insolubilization. N

ll Example 3O U OH 7 Same reactions as Example l-U except that 1 mol ofHO methyl acrylate is substituted for acrylonitrile and 3-0 issubstituted for the N400. Part of this product is thereupon saponifiedwith sodium hydroxide to form the fatty amino acid salt. Furtherexamples of the reaction are summarized in r lar lfatws of aldehyde toPolyamme would the followin table; yield mono or d1 Schiffs base ratherthan a tri Schiffs TABLE IX.OLEFINATION base Such as H H H Moles oiOlefin, C=N(CHzCHgN)5CH2CHzN-CHzCHzN-CHgCHzNHg Compound Olefin Mole ofPolyamine Time Temper- HO CH2 N-400 or Polyature,

amine N400 0. Ha

Derivative Acrylonitrile. 1/1 1 hr 80-100 H H H Methyll lgleth- 1/1 1111'"-.. 80-100 C=N(CHzCH2N)5CH2CHzN-CHzCHzN-CHzCHzNHz aery a e. -do 3 11hr 80-100 H0 H2 Ethyl oinnamate. 1/1 2 hrs 120 J: Ethyl crotonate 1/1 2hrs.- 120 Hz Di-octyl maleate 1/1 2 hrs 150 Divinyl sulfone.-. 1/2 30min- 90 N Styrene 1/1 30 min 90 Styrene 3/1 30 min" 90 C-H Lauryl meth-3/1 1 hr 120 aerylate. Divinyl sulfone. 1/2 90 OH 4.A3-U1--- Methylmeth-1/1. 100

acrylate. 4A3-Uz Divinyl sulfone 1/2 90 6K1U- Aerylom'trile 2/1 704-A1O1U--- Methylacrylate 1/1 90 I 3; 33 and other isomericconfigurations, such as where the 9-K1U 11% 3g Schiffs base is presenton the branched amino group ZIEQQ II ii 90 rather than on the terminalamino group, etc. 1-O3KU.-- 90 A wide variety of aldehyde may beemployed such as aliphatic, aromatic, cycloaliphatic, heterocyclic,etc., in- The following table presents specific illustration of cludingsubstituted derivatives such as those containing compounds other thanN-400 and its derivatives. aryloxy, halogen, heterocyclic, amino, nitro,cyano, car- TABLE IX-A.OLEFINATION- Mols of Olefin/ Branched M01 ofBranched Example Polyamine Olefin Polyamine or Time 'lemp.,

Branched Poly- C. amine Derivative N800 Acrylonitrile 1:1 -100 N-800Styrene 1:1 80-100 N-800- Divinyl ulone 1:1 80-100 N800 Di-oetylmaleate1:1 125 N1200- Acrylonitrile 2:1 80-100 N1200 Methylaerylate 1:1 80-100N-1200 Ethyl crotonate--- 2:1 120 N1200- Diviuyl sulfone--. 2:1 120Ethyl cinnamate 1 :1 120 Di-octyl maleate- 1 :1 120 Methylmethac- 1:1

rylate. Styrene. 2:1 100 Acrylonitrile 2:1 100 Ethyl cinnamate 1:1 Ethylcrotonate 1:1 Divinyl sulione- 2:1 80 12-O1HU Laurylmethac- 3:1

2544021117..-- 1:1 90 1:1 90 4:1 90 21 90 25-A102HKU 1:1 90

boxyl, etc. groups thereof. Non-limiting examples are the following.

Aldehydes:

Benzaldehyde Z-methylbenzaldehyde 3 -met-hylbenz aldehy de4-methylbenzaldehyde Z-methoxybenzaldehyde 4-methoxybenzaldehydea-naphthaldehyde b-naphthaldehyde 4-pheny-lbenzaldehyde Propionaldehyden-Butyraldehyde Heptaldehyde Aldol 2-hydroxybenzaldehyde2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3-methoxybenzaldehyde2-4-dihydroxybenzaldehyde 2-6-dihydroxybenzaldehyde2-hydroxynap-hthaldehyde-1 1-hyd-roxynaphthaldehyde-ZAnthrol-2-aldehyde-1 2-hydroxyfluorene-aldehyde-14-hydroxydiphenyl-aldehyde-3 3-hydroxyphenanthrene-aldehyde-41-3-dihydroxy-2-4-dialdehydebenzene 2-hydroxy-5 -ch-lorobenzaldehyde2-hydroxy-3 :5 -dibromobenzaldehyde 2-l1ydroxy-3 -nitr-obenzaldehyde2-hydroxy-3-cyanobenzaldehyde 2-hydroxy-3-carboxybenzaldehyde4-hydroxypyridine-aldehyde-3 4-hydroxyquinoline-aldehyde-3 7-hydroxyquinoline-aldehyde-8 Formaldehyde Glyoxal Glyceraldehyde Schiifsbases are prepared with the polyamines of this invention in aconventional manner such as described in Synthetic Organic Chemistry byWagner & Zook (1953, Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be morecomplex wherein the carbonyl reactant instead of reacting intramolecularly in the case of a Schiifs base may react in'termolecularlyso as to act as a bridging means between two or more polyaminocompounds, thus increasing the molecular weight of the polyamine asschematically shown below in the case where formaldehyde is the carbonylcompound:

In addition to increasing the molecular Weight by means of aldehydes,these compounds result in the formation of cyclic compounds.

Probably both molecular weight increase and cyclization occur during thereaction.

The following examples illustrate the reaction of carbonyl compoundswith branched polyamines. The symbol employed to designate carbonylationis C, acylation, carbonylation AC, and alkylation, carbonylation KC.

Example 1-C Charge 400 grams of N-400 and 400 grams of xylene hyde (1mol).

Hold at this temperature for 2 hours.

Vacuum is then applied until all xylene is stripped off. The reactionmass is a thick dark liquid which is soluble in water.

Examlple 6-C Using the same apparatus as above, charge '400 grams ofN-400. While stirring, add slowly at room temperature 82 grams of 37%aqueous formaldehyde (1 mol of HCHO).

This reaction is exothermic and the temperature must be controlled withan ice bath. After the exoviscous water-soluble material.

thermi-c reaction has ceased, raise temperature to 100 C. The reactionmass may be stopped at this point.

It is a However, it is possible to continue heating under vacuum untilall of the water has been eliminated. Cross-linking occurs with thisprocedure and care must be taken to prevent insolubilization.

Further examples of this reaction are summarized in the following table:

TABLE X.CARBONYLATION Compound A dehyde M01. Temp., Time Ratio C.

Salieylaldehyde 1/1 120 2 hrs. d0 2/1 120 2 hrs.

.do 3/1 120 2hrs. 2-hydroxy-3-methoxy- 1/1 130 4 hrs.

benzaldehyde.

d 2/1 130 4 hrs. 3/1 130 4 hrs. 5/1 130 4 hrs. 1/1 110 1 hr. 2/1 110 1hr. 3/1 110 1 hr. 311 2 hrs Heptaldehyde 3/1 130 5 hrs Formaldehyde 3/1C) 2 hrs al 2/1 1 hr.

2/1 135 3 hrs 2/1 150 1 hr. 1/1 2 hrs 1/1 120 2 hrs 1/1 120 2 hrs 2/1120 2 hrs *Start 25C. Raise to 100C.

pounds other than N400 and its derivatives.

TAB LE XA.-CA RB ONYLATION Compound Branched Aldehyde Mol Temp, TimePolyamine Ratio C.

N800 Formaldehyde 2: 1 80 1 hour N-800 d0 1:1 80 Do. 0. 5: 1 80 Do. 2: 1100 Do. 1:1 100 Do. do 0. 5:1 100 D0. Salicylaldehyde 3: 1 120 Do. .do2:1 120 Do. o 1:1 120 D0. Benzaldehyde. 3:1 110 Do. do 2:1 110 Do. .d 1:1 110 Do. 10OaAC Glyoxa 1:1 105 Do. 24OzAC- d0. 0.5:1 105 D0. 12O1HC do0.25:1 105 Do. 26-A10z0 G1yceraldehyde. 1 1 2 hours 10U C d0 05:1 130D0. 11-U C Furluraldehyde 1: 1 80 1 hour 12O1HUC d0 0.5:1 80 Do.

' 2a The examples presented above are non-limiting examples. It shouldbe clearly understood that various other combinations, order ofreactions, reaction ratios,

Example designation: Meaning (1) A Acylated. (2) A Acylated thenoxyalkylated. (3) AOA Acylated, then oxyalkylated then acrylated. (4)AOH Acylated, then Oxyalkylated, then heat treated. (5) AX Salt orquaternary of (1). (6) AOX Salt or quaternary of (2). (7) AOAX Salt orquaternary of (3). (8) AOHX Salt or quaternary of (4). (9) OOxyalkylated. (10) 0A Oxyalkylated, then acylated. (11) OH Oxyalkylated,then heat treated. (12) K Alkylated. 4 (13) KX Salt or quaternary of(12). (14) KA Alkylated, then acylated. (15) AK Acylated, thenalkylated. (16) AKX Salt or quaternary of (15). (17) OK Oxyalkylated,then alkylated. (18) OKX Salt or quaternary of (17). (19) CCarbonylated. (20) AC Acylated, then carbonylated. (21) KC Alkylated,then carbonylated. (22) CO Carbonylated, then oxyalkylated. (23) UOlefinated (24) AU Acylated, then Olefinated. (25) KU Alkylated, thenOlefinated. (26) KUX Salt or quaternary of (25 USE AS A CHELATIN G AGENTThis phase of the invention relates to the use of the compounds of ourinvention as chelating agents and to the chelates thus formed.

Chelation is a term applied to designate cyclic structures arising fromthe combination of metallic atoms with organic or inorganic molecules.or ions. Chelates are very important industrially because one of theunusual features of the chelate ring compounds is their unusualstability in which respect they resemble the aromatic rings of organicchemistry. Because of the great afiinity of chelating compounds formetals and because of the great stability of the chelates they form,they are very important industrially.

' vention are useful as bactericidal and fungicidal agents,

particularly in the case of the copper chelates. In addition thechelates can be employed to stabilize hydrocarbon oils against thedeleterious effects of oxidation.

In general, these chelates are prepared by adding a sufiicient amount ofa metal salt to combine with a compound of this invention. They areprepared by the general method described in detail by Hunter andMarriott in the Journal of the Chemical Society (London) 1937, i

2000, which relates to the formation of chelates from metal ions andsalicylidene imines.

The following examples are illustrative of the preparation of thechelates.

Example 8-A To a solution of 0.1 mole of the chelating agent of Example8-A in alcohol is added 0.1 mole of cupric acetate monohydrate. Aftermost of the alcohol is evaporated, a green solid precipitates whichanalysis indicates to be the copper chelate.

Example 6-K The above procedure is used except the cobaltous acetatetetrahydrate is employed to yield a red solid which analysis indicatesto be the cobaltous chelate.

Example 4A C The, above procedure is used except that nickelous acetate,Ni(OAC) -4H O is employed. A dark green product is formed.

To save repetitive detail, chelates are formed from the above nickel,cobalt and copper salts, and the compounds shown in the following table.

CHELATING AGENTS AGENTS FOR SCALE PREVENTION This phase of the inventionrelates to the use of the compounds of this invention in a process forremoving from surfaces, particularly of pipes and other processingequipment, deposits of inorganic solids arising from the passage ofaqueous media therethrough, and for inhibiting and preventing theaccumulation of such deposits on such surfaces. They are particularlyadapted for use in equipment used in producing and handling crudeoil,,since the water produced from the earth along with the oil oftendeposits inorganic solids as a scale in the well tubing, or, morecommonly, in traps, heaters, or other surface equipment, and in someinstances even in pipelines. They are likewise valuable in controllingdeposits or'scales of such inorganic solids which may accumulate insteam-generating equipment if somewhat hard waters are used. Utility ofthese compounds is not limited to such characteristic applications; theymay be used in other instances where scales or deposits of inorganicsolids originating from naturally-occurring constituents of aqueousmedia constitute a nuisance in industrial or other activities.

The scales or deposits of inorganic solids that occur in hard water withwhich this invention is concerned are clearly to be distinguished fromaccumulations of solid organic matter, whose removal is thesubject-matter of Patent No. 2,470,831, dated May 24, 1949.

The accumulations with which this phase of the present invention isconcerned are also to be distinguished at the outset from accumulationsof mud solids in the form of mud sheaths. Mud sheaths are essentiallyfilter cakes of water-insoluble solids of natural clay solids or ofbarite, iron oxide, bentonite, or other inorganic solids used inpreparing and conditioning drilling mud and originally present as anaqueous suspension. The inorganic solids with which the presentinvention is concerned may be though-t of as being originallywater-soluble inorganic solids which have been precipitated ashard-water scale by the application of heat, the loss of carbon dioxideor or some other constituent, or in some cases by the chilling of theaqueous medium as it passes through the conduit or apparatus whichexhibits the scaling, etc. Accumulations of such solids are recurringproblems.

The process which constitutes this phase of our invention consists inapplying to inorganic solid deposits of the kind described the compoundsof the present invention to the end that such inorganic solids areremoved from the surfaces to which they originally adhered. By suchmeans, the capacity of pipes, towlines, pipelines, traps, tanks, pumps,and other equipment supporting such deposits is materially increased.The exact nature of the action taking place when our reagents are usedin unknown to us.

It will be apparent that if our reagents are applied to a system whichperiodically accumulates, such deposits of inorganic solids, beforeappreciable deposition has occurred, and if such application of reagentsis practiced continuously or with sufficient frequency, the operationmay be considered a preventive process, rather than a corrective one. Ifapplied in somewhat insuflicient quantity to a deposit alreadyaccumulated, it may accomplish partial reduction of such deposit, ratherthan complete removal. Our process is therefore both a preventive and acorrective one, and may be applied in either sense, to achieve the sameultimate goal, viz., improvement of the capacity of conduits throughwhich fluids are passed.

Our process is equally applicable to systems in which a deposit ofinorganic salts is already in existence and to systems which arepotentially susceptible to such deposition. When we use the wordinhibiting, we mean to include therein the prevention, reduction, andremoval of such deposits of inorganic solids.

These compositions are usually used diluted with a suitable diluent,such as water or a water-insoluble organic liquid capable of acting asan oil solvent.

In treating systems in which oil is present, we prefer to mix thecompounds with a water-insoluble organic liquid capable of acting as anoil solvent, and to employ such mixture in the form of a relativelystable aqueous dispersion. By relatively stable aqueous dispersion, wemean one that is not resolved into its components spontaneously onstanding for protracted periods of time, e.g., for more than one hour.However, such preferred mixture may be employed undiluted or dispersedin oil. These compounds may be mixed with water, especially if in saltform, to produce a relatively stable aqueous dispersion, and may be usedas such or diluted further with water. In general, we believe the formof the reagent in which a water-insoluble organic liquid is incorporatedgives superior results, at least where the system to be treated includesoil.

Some of the compounds of our invention are freely dispersible in waterin the free state. In other instances, the free forms of the reagentsare substantially waterinsoluble, but the salt forms (e.g., theacetates) are very water-dispersible. In such cases We prefer to employthe water-dispersible form by neutralizing the compound to produce asalt which will be water-dispersible. We have found, for example, thatthe acetate, hydroxyacetate, lactate, gluconate, propionate, caprate,phthalate, fumarate, maleate, benzoate, succinate, oxalate, tartarate,chloride, nitrate, or sulfate, prepared by addition of the suitable acidto the compound, usually constitutes a reagent which is somewhat moresoluble or dispersible in water than many of the original compounds. Itis to be understood that references to thereagents, in these speci- 32fications and claims, include the reagent in the form of salts, as wellas in the free form and the hydrated form.

Depending upon the choice of compound and its molecular weight, thesolubility may be expected to range from ready water-solubility in thefree state substantially to water-insolubility. As stated above, thesalts, and specifically the acetates, generally show improvedwater-solubility over the simple compound and we have obtained the bestresults by using salt forms which possess appreciable water-solubility.

For a number of reasons it is usually desirable to mix the compoundswith a suitable diluent before use in our process. Water is sometimesthe most desirable diluent, being cheap and available. In someinstances, as above noted, especially where the scale-susceptible systemincludes oil we prefer to use a water-insoluble organic liquid, which iscapable of acting as an oil solvent, for the diluent. Many materialslend themselves to this use. One of the most common is the aromaticfraction of petroleum distillates. Edeleanu extract, which comprisesaromatic a-nd unsaturated compounds, is frequently found useful. In somecases stove oil or a similar petroleum distillate is usable. Oilsolvents like carbon tetrachloride or carbon disulfide are usable,although their comparatively high cost militates against their use.Amylene dichloride is sometimes a desirable material for the presentpunpose, as are tetrachloroethane, tetraline, trichloroethylene, benzoland its homologs, cyclohexane, etc. This component of our reagentsshould naturally be compatible with the other ingredient thereof;otherwise its selection is not limited. Cost and availability willinfluence the selection. We prefer to use an aromatic petroleum solventas a widely available reagent of good properties and low cost for thepresent use.

To prepare our reagents, when diluents are included, the components. aresimply mixed together in suitable proportions. The optimum proportion ofeach will vary, depending on its properties; but in general theresulting mixture should be homogeneous.

We also require that the finished reagent produce a relatively stableaqueous dispersion. In cases where the ingredients form thoroughlyhomogeneous mixtures which are not water-dispersible, the transformationof the reagent into its salt form will sometimes accomplish thispurpose. In such cases, we have preferably used acetic acid to effectthis neutralization.

The reagent may be employed in undiluted form, except for the dilutionemployed in manufacture, to deliver it in readily usable form. In suchcases, the reagent as compounded is simply introduced into the pipe orapparatus from whose surface a deposit or scale of inorganic solids isto be removed or deposition thereon inhibited. In such cases, there isundoubtedly produced an aqueous dispersion of the reagent if water ispresent in or passing through such apparatus. Such addition of undilutedreagent into a stream containing aqueous components may be consideredequivalent to introducing a previously prepared aqueous dispersion of myreagent.

In most cases, an aqueous dispersion is obtained almost spontaneously onmixing with water our reagents and preferred non-aqueous diluent. Weprefer to employ such embodiments of our reagents in aqueous dispersion,because, when so employed, the components of the reagent are preventedfrom separating from each other by the influence of oily materialspresent in the pipe or apparatus to be treated.

When a water-insoluble organic liquid is employed as diluent inpraparing our reagents, we prefer to employ a considerable excess ofreagent over what would be exactly required to effect dispersion of thewater-insoluble organic liquid in water. Such excess further preventsany separation of the phases, enhancing the stability of the dispersionso that it will remain stable for at least several hours. The excess ofreagents also acts to lower the surface tension of the whole reagent,because of which 33 the reagent exhibits a marked penetrating effect. Inthis way, it is carried into the crevices and irregularities of thedeposit, weakening the bond between the deposit of inorganic solids andthe supporting wall.

As a preferred example of reagent, we employ a 20% by weight dispersionin aromatic petroleum solvent, including 2% by weight of concentratedacetic acid in the finished reagent in some instances. We prefer toemploy this reagent in the form of a dilute aqueous dispersion, of about5% by weight concentration. Sometimes aqueous dispersions containing aslittle as 1% of the reagent are fully effective. Sometimes it isdesirable to introduce the reagent in the form of a more concentratedaqueous dispersion, as when additional water is expected to beencountered in the system being treated. This preferred reagent may ofcourse be introduced in undiluted IfOIIII, if desired, it has beensuccessfully so used.

From the foregoing, it will be understood that our process, broadlystated, consists in subjecting a deposit of inorganic solids of the kinddescribed above to the action of a reagent of the kind described. Merelyintroducing our rea'gent continuously into a scaled-up system usuallyresults in the more or less complete removal of the scale within areasonable time. Agitating the reagent in the system sometimes facilitesremoval of the scale deposits, as does allowing the reagent to stand inthe system and soak it for any desired time.

The theory of the mode of operation of our process is uncertain; but theeffects of applying the process are striking. Capacity of pipes andapparatus is usually promptly and markedly increased. Line pressureswhich have increased with deposition of the inorganic solids fall tonormal within a short time; and sometimes sizeable chunks of thedislodged deposit are observed in the stream from the wells or lines, onscreens inserted into such streams for purposes of observation, or even,at times, by their erosive effects on valves or other equipment downstream the deposit. 7

Our reagents may be applied in many ways, depending on the location andcharacter of the deposit of inorganic solids it is proposed to remove orwhose deposition is to be inhibited. In the case of pipe, it is usuallypreferred to introduce, by means of a small pr-oportioning pump, acontinuous small stream of reagent, either undiluted or diluted asdesired, upstream the deposit, until the latter is dislodged andremoved. In some apparatus, it is most practicable to fill the Wholewith an aqueous solution or dispersion of the reagent, and allow aconsiderable.

soaking period to elapse before again pumping. As stated above, weprefer to introduce our reagents in aqueous dispersion, and continuouslyin small proportions, to inhibit or to remove inorganic solid depositsof the kind here under consideration. The essential step of our processis that our reagent is brought into contact with the deposit; and thelatter is thereby caused to become dislodged from its supportingsurface.

The following specific examples will illustrate typical applications ofour process.

Example 3-0 The surface flow system from an oil well regularlyaccumulates a hard scale which includes an appreciable proportion ofcarbonates precipitated from the oil well water as a compact, adherentdeposit, reaching thicknesses of A or greater, in the header manifolds,trap valves, rundown lines, etc. Trap valves at the highand low-pressuretraps are favorable observation points, in that they scaleup soonestafter cleaning; General practice at the location is to produce the wellas long as possible, shut down, and then remove the scale manually fromall accessible locations in the system. The operation is required to berepeated at intervals of about three weeks.

A reagent comprising a 20 weight percent solution of compound 3-0 of thefollowing table in an aromatic sols,25s,42 s

vent is introduced continuously into the system upstream thehigh-pressure trap at the rate of 1 gallon to 1,500 barrel of waterproduced by the well. Inspection of accessible points, which normallyscale-up within three weeks, is made regularly from the beginning ofsuch application of reagent. After about a month, inspection shows aslight deposit of solids on the trap valves, very soft and readilyremovable. Three months later, the injection of reagent is stillcontinuing, the well having never been shut down for scale removal, andthere is no evidence of appreciable scale accumulation in the system.

Example 3-A This example is cited to illustrate the removal approach,rather than the inhibition or prevention approach of the previousexample.

An' oil well production system has accumulated scale to the point Whereit could handle only about 9,000 barrels of fluid daily, against a ratedcapacity of 12,000 barrels daily. Any attempt to increase the flowthrough the traps caused them to pop their contents of crude oil. Thecompound of 3A (20 weight percent solution in aromatic solvent) isinjected at the well head, just downstream the flow beam, afterpreliminary inspection of the degree of scale deposition has been made.tion shows that flow valves upstream the master trap, the manifold, andalso the trap discharge valve are heavily scaled. The rate of reagentfeed is 1 gallon to 1,500 barrels of well water. Within a week afterintroduction of our reagent ha begun, sustained unrestricted flow at12,000 barrels daily is again effected.

Re-inspection of accessible points shows some of them to be entirelyfree from scale deposits, points previously scaled hard. In other cases,the scale has not been entirely removed in the short time of applicationof our reagent; but the remaining accumulations are very soft incharacter.

This second example illustrates the fact that our process may besuccessfully applied as a scale-removing process; and the fact thatincomplete removal is found at several points in the system after ashort period of treatment illustrates the scale-reduction feature of ourprocess.

Examples 6-0 14 In a third application of our process, we employcompound 6-O A in the form of the acetate, prepared as a 20 weightpercent aromatic solvent solution diluted with water to a 15% solution.This material is introduced into a pipe carrying oil and water at therate as in the preceding two examples. Such introduction effectivelyinhibits the accumulation of scale in such pipe.

Examples of compounds capable of being similarly employed are shown inthe following table.

SCALE REMOVER Such inspec-v NH: y

wherein R is an alkylene group having at least two carbon atoms, x is aninteger of 4 to 24, y is an integer of 1 to 6, and z is an integer of-6,

(2) an acylated branched polyalkylenepoly-amine containing at leastthree primary amino groups and at least one tertiary amino group andhaving the formula NH: y wherein R is an alkylenegroup having at leasttwo carbon atoms, x is an integer of 4 to 24, y is an integer of'l to 6,and z is an integer of 0-6, formed by reacting, at a temperature of fromabout 120 C. to about 300 C., said polyalkylenepolyamine with a compoundselected from the group consisting of (i) a carboxylic acid having 7-39carbon atoms and (ii) a precursor of said carboxylic acid capable offorming said acid in said reaction, (3) an oxyalkylated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula i NHa-(R RN--RNHa 36 wherein R is an alkylene group having at least two carbon atomsx is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 06, formed by reacting, at a temperature of fromabout C. to about 200 C. and a pressure of from about 10 p.s.i. to about200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having atleast 2 carbon atoms,

(4) an alkylated branched polyalkylenepolyamine containing at leastthree primary amino groups and at least one tertiary amino group andhaving the for- R1TI- RNH:

w 1 i NH: Y wherein R is an alkylene group having at least two carbonatoms, x is an integer of 4 to 24, y is an integer of 1 to 6, and z isan integer of O-6, formed by reacting, at a temperature of from about C.to about 250 C., said polyalkylenepolyamine with a hydrocarbon halidealkylating agent having 1 to 30 carbon atoms, (5) an olefinated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula l NHz y whereinR is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of fromabout 70 C. to about 100 C., said polyalkylenepolyamine with anolefinating agent selected from the group consisting of acrylonitrile,styrene, butadiene, vinyl ethers and vinyl sulfones,

(6) a Schiif base reaction product of a branched polyalkylenepolyaminecontaining at least three primary amino groups and at least one tertiaryamino group and having the formula NH: V wherein R is an alkylene grouphaving at least two carbon atoms,

x is an integer of 4 to 24, y is an integer of 1 to 6, and z is aninteger of 06,

formed by reacting said polyalkylenepolyamine with a compound selectedfrom the group consisting of aldehydes and ketones,

(7) an acylated, then oxyalkylated branched polyal- 38 amino group andhaving the hereinabove recited formula, formed by reacting, at atemperature of from about 120 C. to about 300 C., saidpolyalkylenepolyamine with an acylating agent selected from thekylenepolyamine containing at least three primary group consisting of(i) a carboxylic acid having 7-39 amino groups and at least one tertiaryamino group carbon atoms and (ii) a precursor of said carboxylic andhaving the hereinabove recited formula, formed acid capable of formingsaid acid in said reaction, by reacting, at a temperature of from about125 C. and then reacting said acylated polyalkylenepolyto about 300 C.,said polyalkylenepolyamine with amine with a compound selected from thegroup conan acylating agent selected from the group consist- 10 sistingof aldehydes and ketones, ing of (i) acarboxylic acid having 7-39 carbonatoms (13) a Schiff base reaction product of an alkylated and (ii) aprecursor of said carboxylic acid capable branched polyalkylenepolyaminecontaining at least of forming said acid in said reaction, and thenrethree primary amino groups and at least one tertiary acting saidacylated polyalkylenepolyamine, at a temamino group and having thehereinabove recited for perature of from about 80 C. to about 200 C. and15 mula, formed by reacting, at a temperature of from a pressure of fromabout 10 p.s.i. to about 200 p.s.i., about 100 C. to about 250 C., saidpolyalkylenewith an alkylene oxide having at least 2 carbon atoms,polyamine with a hydrocarbon halide alkylating (8) an oxyalkylated, thenacylated branched polyalkylagent having 1-30 carbon atoms, and thenreacting enepolyamine containing at least three primary amino saidalkylated polyalkylenepolyamine with a comgroups and at least onetertiary amino group and pound selected from the group consisting ofaldehaving the hereinabove recited formula, formed by hydes and ketones,reacting, at a temperature of from about 80 C. to (14) an oxyalkylatedSchifi base reaction product of about 200 C. and a pressure of fromabout 10 p.s.i. a branched polyalkylenepolyamine containing at least toabout 200 p.s.i., said polyalkylenepolyamine with three primary aminogroups and at least one tertiary an alkylene oxide having at least 2carbon atoms amino group and having the hereinabove recited and thenreacting said oxyalkylated polyalkyleneformula, formed by reacting saidpolyalkylenepolypolyamine, at a temperature of from about 120 C. aminewith a compound selected from the group conto about 300 C., with anacylating agent selected sisting of aldehydes and ketones to form saidSchiif from the group consisting of (i) a carboxylic acid base reactionproduct and then reacting said Schiif having 7-39 carbon atoms and (ii)a precursor of base reaction product, at a temperature of from saidcarboxylic acid capable of forming said acid in about 80 C. to about 200C. and a pressure of from said reaction, about 10 p.s.i. to about 200p.s.i., with an alkylene (9) an alkylated, then acylated branchedpolyalkyleneoxide having at least 2 carbon atoms,

polyamine containing at least three primary amino (15) an acylated, thenolefinated branched polyalkylgroups and at least one tertiary aminogroup and enepolyamine containing at least three primary amino havingthe hereinabove recited formula, formed by groups and at least onetertiary amino group and reacting, at a temperature of from about 100 C.to having the hereinabove recited formula, formed by about 250 C., saidpolyalkylenepolyamine with a reacting, at a temperature of from about120 C. to hydrocarbon halide alkylating agent having 1-30 car- I about300 C., said polyalkylenepolyamine with an bon atoms, and then reactingsaid alkylated polyal- 40 acylating agent selected from the groupconsisting of kylenepolyamine, at a temperature of from about (i) acarboxylic acid having 7-39 carbon atoms and 120 C. to about 300 C.,with an acylating agent '(ii) a precursor of said carboxylic acidcapable of selected from the group consisting of (i) a carboxformingsaid acid in said reaction, and then reacting ylic acid having 7-39carbon atoms and (ii) a presaid acylated polyalkylenepolyamine, at atemperacursor of said carboxylic acid capable of forming said mm of fromabout 70 C. to about 100 C., with an acid in said reaction, olefinatingagent selected from the group consisting (10) an acylated, thenalkylated branched polyalkylof acrylonitrile, styrene, butadiene, vinylethers and enepolyamine containing at least three primary amino vinylsulfones, and groups and at least one tertiary amino group and (16) analkylated, then olefinated branched polyalkylhaving the hereinaboverecited formula, formed by enepolyamine containing at least threeprimary amino reacting, at a temperature of from about 120 C. groups andat least one tertiary amino group and to about 300 C., saidpolyalkylenepolyamine with having the hereinabove recited formula,formed by an acylating agent selected from the group consistingreacting, at a temperature of from about 100 C. to of (i) a carboxylicacid having 7-39 carbon atoms about 250 C., said polyalkylenepolyaminewith a hyand (ii) a precursor of said carboxylic acid capable 5drocarbon halide alkylating agent having from 1-30 of forming said acidin said reaction, and then recarbon atoms, a then reacting Saidalkylated P yacting said acylated polyalkylenepolyamine, at atemalkylefiepolyamine, at a temperature f f m a t perature of from about100 C. to about 250 C., to a ut C, Wit n l finati g ag nt 86- with ahydrocarbon halide alkylating agent having 1- lected from the groupConsisting of acrylonitrile, 30 rbo t styrene, butadiene, vinyl ethersand vinyl sulfones.

(11) an oxyalkylated, then alkylated branched polyal- 2. The process ofclaim 1 wherein the compound is a kylenepolyamine containing at leastthree primary branched polyalkylenepolyamine containing at least threeamino groups and at least one tertiary amino group P y amino groups andat least 0116 tertiary amino and having the hereinabove recited formula,formed g oup and having the formula by reacting, at a temperature offrom about 80 C. H to about 200 C. and a pressure of from about 10 I fp.s.i. to about 200 p.s.i., said polyalkylenepolyamine i with analkylene oxide having at least 2 carbon 1 7 R IlYHa Y atoms, and thenreacting said oxyalkylated polyalkylenepolyamine, at a temperature offrom about 100 C. to about 250 C., with a hydrocarbon halide alkylatingagent having 1-30 carbon atoms,

(12) a Schiff base reaction product of an acylated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary wherein R is an alkylene group having at least twocarbon atoms,

39 x is an integer of 4 to 24, y is an integer of 1 to 6, and z is aninteger of -6.

3. The process of claim 1 wherein the compound is an acylated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula II NHn-(R- RlTIRNHz I'c T z y wherein R is an alkylene group having at least two carbonatoms x is an integer of 4 to 24 y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting, at a temperature of from about 120 C. to about 300C., said polyalkylenepolyamine with a compound selected from the groupconsisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) aprecursor of said carboxylic acid capable of forming said acid in saidreaction. 4. The process of claim 1 wherein the compound is an L NH: y

R is an alkylene group having at least two carbon atoms x is an integerof 4 to 24 y is an integer of 1 to 6, and

z is an integer of 0-6,

wherein formed by reacting, at a temperature of from about 80 C. toabout 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i.,said polyalkylenepolyamine With an alkylene oxide having at least twocarbon atoms.

5. The process of claim 1 wherein the compound is an alkylated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula RN RNHz i [la].

NH: y

wherein R is an alkylene group having at least two carbon atoms x is aninteger of 4 to 24 y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting, at a temperature of from about 100 C. to about 250C., said polyalkylenepolyamine with a hydrocarbon halide alkylatingagent having 1 to 30 carbon atoms.

6. The process of claim 1 wherein the compound is an olefinated branchedpolyalkylenepolyamine containing at least three primary amino groups andat least one tertiary amino group and having the formula NH2 y wherein Ris an alkylene group having at least two carbon atoms x is an integer of4 to 24 y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting, at a temperature of from about 70 C. to about C.,said polyalkylenepolyamine with an olefinating agent selected from thegroup consisting of acrylonitrile, styrene, butadiene, vinyl ethers andvinyl sulfones.

7. The process of claim 1 wherein the compound is a Schifi base reactionproduct of a branched polyalkylenepolyamine containing at least threeprimary amino groups and at least one tertiary amino group and havingthe formula H wins) mma i NH: V wherein R is an alkylene group having atleast two carbon atoms x is an integer of 4 to 24 y is an integer of 1to 6, and

z is an integer of 0-6,

formed by reacting said polyalkylenepolyamine with a compound selectedfrom the group consisting of aldehydes and ketones.

8. The process of claim 1 wherein the compound is an acylated, thenoxyalkylated branched polyalkylenepolyamine containing at least threeprimary amino groups and at least one tertiary amino group and havingthe formula R is an alkylene group having at least two carbon atoms x isan integer of 4 to 24 y is an integer of 1 to 6, and

z is an integer of 0-6,

wherein formed by reacting, at a temperature of from about I C. to about300 C., said polyalkylenepolyamine with an acylating agent selected fromthe group consisting of (i) a carboxylic acid having 7-39 carbon atomsand (ii) a precursor of said carboXylic acid capable of forming saidacid in said reaction, and then reacting said acylatedpolyalkylenepolyamine, at a temperature of from about 80 C. to about 200C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with analkylene oxide having at least 2 carbon atoms.

(References on following page)

1. A PROCESS FOR PREVENTING, REDUCING AND REMOVING THE DEPOSITION OFHARD WATER SCALE FROM THE SURFACES OF EQUIPMENT OF AN AQUEOUSSCALE-FORMING MEDIA SYSTEM WHICH IS CHARACTERIZED BY SUBJECTING SAIDSYSTEM TO THE ACTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF(1) A BRANCHED POLYALKYLENOPOLYAMINE CONTAINING AT LEAST THREE PRIMARYAMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THEFORMULA